2,3-dimethyl-3-hydroxybutanal | 94284-08-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2,3-dimethyl-3-hydroxybutanal
• 英文别名: (R)-3-hydroxy-2,3-dimethylbutanal；(2R)-3-hydroxy-2,3-dimethylbutanal
• CAS: 94284-08-9
• 化学式: C₆H₁₂O₂
• 分子量: 116.16
• InChiKey: IMELMGSFBHXINN-YFKPBYRVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.2
• 重原子数：
  8
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  37.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2,3-dimethyl-3-hydroxybutanal 在 正丁基锂 、 水 、 mercuric triflate 、 对甲苯磺酸 作用下， 以 四氢呋喃 、 正己烷 、 乙腈 为溶剂， 反应 3.17h， 生成 (3α,5α,11β,17ξ,22S,24S)-3,11-bis(benzyloxy)-24-methyl-22,25-epoxyfurostan-20-ol
  参考文献：
  名称：

  Synthesis of the Antiproliferative Agent Hippuristanol and Its Analogues via Suárez Cyclizations and Hg(II)-Catalyzed Spiroketalizations

  摘要：

  A full account of the synthesis of hippuristanol and its analogues is described. Hecogenin acetate was identified as a suitable and economical starting material for this work, and substrate-controlled stereo-selection was obtained throughout the construction of the key spiroketal unit. Suarez cyclization was first used, but Hg(II)-catalyzed spiroketalization of the 3-alkyne-1,7-diol motif was finally identified as the most convenient strategy.

  DOI：

  10.1021/jo102054r
• 作为产物：
  描述：

  (2S)-2,3-二甲基-1,3-丁二醇 在 sodium hypochlorite 、 2,2,6,6-四甲基哌啶氧化物 、 potassium bromide 作用下， 以61%的产率得到2,3-dimethyl-3-hydroxybutanal
  参考文献：
  名称：

  有效合成3-TBDMS-11α，25-二羟基维生素D3和D2醚。

  摘要：

  维生素D缺乏症可能导致多种人类疾病。作为适当诊断和治疗的先决条件，必须最准确，高度特异性地测定与医学相关的维生素D代谢产物。已经证明，通过C11处的羟基连接的维生素D缀合物对于开发用于竞争性蛋白质结合测定中的高特异性抗体可能是有希望的。描述了从维生素D2开始的500毫克规模的3-TBDMS-11α，25-二羟基维生素D3和D2醚的连接合成。为了在C11处安装羟基，使用Pd（OAc）2介导的烯酮的氧化，环氧化和随后的环氧化物开环的序列，以获得合适的CD环前体，其通过以下方式与A环二苯基膦氧化物连接： Wittig-Horner反应。

  DOI：

  10.1016/j.jsbmb.2020.105638

文献信息

• NEW SYNTHONES FOR PREPARATION OF 19-NOR VITAMIN D DERIVATIVES
  申请人：Chodynski Michal

  公开号：US20130006003A1

  公开（公告）日：2013-01-03

  The present invention discloses the synthone of Formula (I), wherein R 1 and R 2 are the same or different and represent independently hydrogen atom or hydroxyl protecting group, and its use for preparation of 19-nor vitamin D derivatives of general Formula (IV), wherein represents single or double bond, p represents an integer 0 to 3, R 1 and R 2 represent independently hydrogen atom or hydroxyl protecting group, R 3 represents hydrogen atom, CH 3 or hydroxyl group, R 4 , R 5 and R 6 represent independently hydrogen atom, C 1 -C 3 -alkyl or hydroxyl group or two of R 4 , R 5 and R 6 substituents altogether form cyclopropyl group, in particular for preparation of paricalcitol.

  本发明揭示了公式（I）的合成物，其中R1和R2相同或不同，分别独立表示氢原子或羟基保护基，以及其用于制备一般公式（IV）的19-去维生素D衍生物，其中表示单键或双键，p表示整数0至3，R1和R2分别表示氢原子或羟基保护基，R3表示氢原子、CH3或羟基，R4、R5和R6分别表示氢原子、C1-C3-烷基或羟基，或R4、R5和R6中的两个取代基共同形成环丙基，特别用于制备帕立卡钙。
• Efficient Synthetic Approach to Potent Antiproliferative Agent Hippuristanol via Hg(II)-Catalyzed Spiroketalization
  作者：Kontham Ravindar、Maddi Sridhar Reddy、Lisa Lindqvist、Jerry Pelletier、Pierre Deslongchamps

  DOI：10.1021/ol1019663

  日期：2010.10.1

  The steroidal natural product hippuristanol targets eukaryotic translation initiation factor (eIF)4A which plays a pivotal role in translation in eukaryotic cells. Now an efficient synthesis of hippuristanol from 11-ketotigogenin is reported. The synthesis features a rapid construction of a spiroketal unit via Hg(OTf)2-catalyzed oxidation/spiroketalization of the 3-alkyn-1,7-diol motif.

  类固醇天然产物hippuristanol靶向真核翻译起始因子（eIF）4A，该因子在真核细胞的翻译中起关键作用。现在已经报道了由11-酮基生成素有效合成马尿嘌呤醇。该合成的特征是通过Hg（OTf）2催化3-炔基1,7-二醇基序的氧化/螺缩酮化作用来快速构建螺缩酮单元。
• Process for preparation of paricalcitol and intermediates thereof
  申请人：Formosa Laboratories, Inc.

  公开号：US07491712B1

  公开（公告）日：2009-02-17

  The invention relates to a novel process for the preparation of Paricalcitol and intermediates thereof.

  本发明涉及一种制备帕利卡钙及其中间体的新工艺。
• Synthesis and crystallographic study of 1,25-dihydroxyergocalciferol analogs
  作者：Anita Pietraszek、Maura Malińska、Michał Chodyński、Małgorzata Krupa、Krzysztof Krajewski、Piotr Cmoch、Krzysztof Woźniak、Andrzej Kutner

  DOI：10.1016/j.steroids.2013.06.001

  日期：2013.10

  The hybrid analogs of 1,25-dihydroxyergocalciferol (PRI-5201 and PRI-5202) were synthesized as potential anticancer agents using a convergent strategy. The analogs were designed by combining a 19-nor modification of the A-ring with the homologated and rigidified ergocalciferol-like side-chain of the previously obtained analogs PRI-1906 and PRI-1907. The strategy also allowed the novel efficient synthesis of 19-nor-1,25-dihydroxyergocalciferol (paricalcitol, PRI-5100) and its (24R)-diastereomer (PRI-5101). The single crystal X-ray structures of the 19-nor analogs (PRI-5100 and PRI-5101) were solved and refined. The A-ring of both analogs adopts exclusively chair beta-conformation in the solid state. The side-chain of these analogs is coplanar with the CD-ring plane, while it is perpendicular in 1,25-dihydroxycholecalciferol. Crown Copyright (C) 2013 Published by Elsevier Inc. All rights reserved.
• An intramolecular Diels-Alder approach to the cis ring fused isomer of the 25-hydroxy vitamin D2 Grundmann ketone
  作者：Stephen R. Wilson、Linda Jacob

  DOI：10.1021/jo00042a014

  日期：1992.7

  Stereospecific Claisen and intramolecular Diels-Alder reactions of chiral ester synthon 4 results in conversion of a single asymmetric center of commercially available ester 4 to a vitamin D synthon, the C/D cis Grundmann ketone 3. The addition of propenyllithium to aldehyde 9 was dominated by a chelated anti-Cram transition state and yielded the threo isomer 12a as the major product. The stereochemistry of 12a was determined by X-ray crystallography. Conversion of benzyl-protected erythro isomer 11b to its dimethylacryloyl ester followed by ester enolate Claisen rearrangement led to the C17 and C20 stereochemistry of vitamin D. Addition of a pentadienyl anion to aldehyde 15 gave a tetraene, 17, which underwent an intramolecular Diels-Alder reaction to produce compound 18. Removal of the C16 hydroxyl and hydrolysis gave only the cis-fused isomer of 3.